JP6089378B2 - Plasma processing equipment - Google Patents

Description

  The present invention relates to a plasma processing method and a plasma processing apparatus that perform plasma processing by bringing plasma into contact with a long object to be processed, and a long object that has been subjected to plasma processing.

  In recent years, many fishing lines have been coated with a resin coating to improve functionality such as colorful paint, thread sliding and flexibility on the surface, and the peeling of the paint and resin material has been suppressed. It has become a challenge.

  As shown in FIG. 14, in the manufacturing process of a fishing line to which painting or resin coating has been applied, first, a resin pellet is formed into a thread shape in step (a). Next, in order to remove dirt and oil adhering to the surface of the undyed yarn in step (b), washing with an aqueous solution containing a surfactant is performed, and subsequently, moisture adhering to the yarn in step (c). Dry to remove. Next, a dyeing solution is applied to the yarn washed in step (d) or dyed by immersing the yarn in the dyeing solution. The dyed yarn is heated in step (e) to fix the dye, and is coated.

  In this manufacturing process, the wettability of the dyeing liquid onto the yarn surface is improved by washing with water in step (a) and drying in step (b) before dyeing the yarn.

  Further, after washing and drying again in step (f), a surface modifier for modifying the surface of the line is applied in step (g), and the functionality of the fishing line is improved in step (h). A resin coating is applied for the purpose.

  In addition to fishing lines, it is common to perform a modification treatment on the surface of the base material in the fiber material manufacturing process, and various methods have been reported. Patent Document 1 describes that surface treatment is performed on synthetic fibers and chemical fibers, cloths, woven fabrics, and nonwoven fabrics made of these using atmospheric pressure glow discharge plasma. According to an embodiment described in Patent Document 1, it is described that a surface of a polyester cloth is hydrophilized by performing an atmospheric pressure glow discharge plasma treatment, thereby flexographic printing with water-based ink on the surface. The effect of making it easy is described.

  Furthermore, it is possible to sterilize or clean the surface of the substrate by bringing the substrate into contact with plasma, and various applications are conceivable.

  In Patent Document 2, a plurality of electrodes are provided on the outer peripheral surface of a cylindrical tube, and a glow discharge plasma is generated in the tube under atmospheric pressure by applying a voltage to the electrodes so as to have a potential difference in the length direction. The device to be made is described.

Patent Document 1: JP-A-6-182195 Patent Document 2: JP-A-4-334543

  However, although plasma treatment is very excellent in surface modification, there is variation in the plasma density distribution in the treatment chamber, and the surface of a cylindrical long object such as a fiber is treated uniformly. It is necessary to provide a certain amount of processing time.

  In addition, when the present inventors conducted an experiment in which plasma treatment was performed on an electrically conductive yarn using the apparatus described in Patent Document 2, abnormal discharge was generated between the electrode and the electrically conductive yarn. Was generated, and plasma was generated so as to cling to the electrically conductive yarn, making it difficult to generate plasma normally. From this experiment, it became clear that it was difficult to perform plasma treatment on the electrically conductive yarn using the apparatus described in Patent Document 2.

  In addition, there is a great demand to perform a modification treatment on the surface of not only fishing lines but also long objects such as fibers and tubes and fabrics made of long objects.

  In order to solve these problems, in the present invention, a plasma having a high density is selectively passed through a plasma having a varied density distribution, so that the plasma can be rapidly applied to a long object. A plasma processing method and a plasma processing apparatus excellent in operability using the plasma processing method and the plasma processing method capable of performing uniform and uniform surface treatment on the surface of a long workpiece while performing the treatment The purpose is to provide a scale.

Flop plasma processing apparatus of the present invention is arranged to face, the highest density near the center of the range to one another overlap in a plan view, gradually density toward the outer circumferential direction is set to the density distribution such that lower plasma A flat plate-shaped upper electrode and lower electrode, and an insulating plate disposed so as to cover at least the entire lower surface of the upper electrode on the lower surface of the upper electrode between the upper electrode and the lower electrode; And a pair which is arranged in parallel with the conveying direction of the long workpiece and supports the insulating plate on the lower electrode in a state where a predetermined gap is formed between the insulating plate and the lower electrode. Spacers and a high-density region of the plasma in the gap, which is provided at least in the center in the conveying direction of the elongated object to be processed. A guide portion that guides so as to travel in a region having a high density, and at a position where the upper electrode and the lower electrode face each other, at least one of the inner surface on the gap side of the insulating plate and the lower electrode The plasma generation gas introduction port for introducing the plasma generation gas into the gap is opened, and the guide portion is one or a plurality of holding portions that form a transport path for a long object to be processed It has a, characterized in that it comprises a rotating device for rotating said elongated of the object to apply a twist in the conveying direction axis with respect to said elongated of the object to be conveyed.

Such, according to the flop plasma processing apparatus of the present invention, by contacting the plasma while advancing the elongated object to be processed to the density of the plasma region having a high relative elongated object to be processed A plasma treatment can be easily performed by contacting a high-density plasma, and a uniform surface treatment can be easily and uniformly applied to the surface of a long object.

  According to the plasma processing method of the present invention, in a plasma with a variation in density distribution, a plasma processing is performed at high speed on a long workpiece by selectively passing a region having a high plasma density, Uniform surface treatment can be performed evenly on the surface of a long workpiece.

  Moreover, according to the plasma processing apparatus of this invention, the plasma processing apparatus excellent in operativity can be provided.

  Furthermore, according to the plasma processing apparatus of the present invention, it is possible to perform effective plasma processing even on a long object to be processed made of a conductive material.

  Furthermore, by using the plasma processing method and the plasma processing apparatus of the present invention, it is possible to obtain a long product having a desired surface modification.

The schematic perspective view which shows the plasma processing apparatus of 1st Embodiment of this invention. FIG. 1 is an enlarged perspective view of a part of the plasma processing apparatus of the present invention shown in FIG. Sectional drawing of the principal part of the plasma processing apparatus of this invention shown in FIG. Schematic cross-sectional view showing the state of a guide section that guides a long object to be processed linearly Schematic cross-sectional view showing a state of guiding a long object to be processed spirally The perspective view which shows the plasma processing apparatus of this invention at the time of connecting a unit cylinder and forming a 1st cylindrical part. The expanded perspective view which cut | disconnected some plasma processing apparatuses of this invention at the time of arrange | positioning an insulating tube The expanded perspective view which cut | disconnected a part of plasma processing apparatus of 2nd Embodiment of this invention. Side view showing a plasma processing apparatus according to a third embodiment of the present invention. The side view which shows the plasma processing apparatus at the time of arrange | positioning two or more 2nd cylindrical parts in 3rd Embodiment of this invention. The side view which shows the plasma processing apparatus of this invention at the time of connecting a unit cylinder and a connection member and forming a 1st cylindrical part and a 2nd cylindrical part. The perspective view which shows the plasma processing apparatus of 4th Embodiment of this invention. It is sectional drawing of the plasma processing apparatus of this invention shown in FIG. 12, (a) is sectional drawing in a longitudinal direction, (b) is BB sectional drawing. Flow chart showing fishing line manufacturing process

  Hereinafter, specific embodiments of the plasma processing method and the plasma processing apparatus of the present invention will be described with reference to FIGS.

  The plasma processing method of the present invention is a method of performing plasma processing by bringing a plasma into contact with a long object to be processed, and there is a variation in the density distribution of the plasma. Plasma treatment is performed on a long workpiece while selectively passing through a region having a high plasma density.

  The long object to be processed includes fibers, twisted yarns, braided yarns, pipes, nanotubes, and combinations thereof, and may be made of any material such as inorganic materials and organic materials. In particular, the inorganic substance is stainless steel, tungsten, steel, and the like, and the organic substance is a polyamide resin, a fluorine resin, a polyester resin, a yarn formed from a polyolefin resin, and a composite yarn thereof.

  Specifically, nylon 6, nylon 66, nylon 12, etc., and polyamide polymers comprising these copolymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene succinate, etc., and polyesters comprising these copolymers Polymers, polyolefin polymers such as polyethylene and polypropylene, fluorine polymers such as polyvinylidene fluoride and polytetrafluoroethylene, acrylic polymers having acrylonitrile as the main chain, polyurethane polymers, and polymers having fiber-forming properties such as polylactic acid A spun yarn composed of monofilament, multifilament and cut fibers thereof, or a composite yarn such as a blended yarn or a blended yarn is used. The diameters of these fibers may be any diameter as long as they do not cause problems such as yarn breakage in the apparatus.

  A first embodiment of the plasma processing apparatus of the present invention using the plasma processing method of the present invention will be described.

  As shown in FIG. 1, the plasma processing apparatus 1 according to the first embodiment of the present invention is provided with a first cylindrical portion 2 formed of a cylindrical tube and an outer peripheral surface of the first cylindrical portion 2 to which power is applied from a power source P. At least two or more ring-shaped electrodes 3 arranged in the longitudinal direction so as to be in close contact with each other, and a plasma generating gas introducing portion 4 for introducing a plasma generating gas into the first cylindrical portion 2 And are provided. When the first cylindrical portion 2 is a cylindrical tube as in the present embodiment, the charges of the ring electrode 3 adjacent to the ring electrodes 3 arranged at least two or more are positive and negative charges. When a voltage is applied with a potential difference in the longitudinal direction so that the alternating currents are alternately arranged, the plasma density distribution varies within the first cylindrical portion 2, and the plasma density near the inner wall where the current density is high The density is the highest and the density of the plasma decreases as it approaches the central portion in the radial direction, and a uniform density distribution appears in the longitudinal direction of the first cylindrical portion 2.

  As shown in FIG. 2, a guide portion 5 including a plurality of disk-shaped guide members 5 a disposed in the longitudinal direction of the first tubular portion 2 is provided inside the first tubular portion 2. Yes. As shown in FIG. 3, the guide member 5 a has a smaller diameter than the guide member 5 a in the region where the plasma density appears inside the first cylindrical portion 2, that is, in the vicinity of the inner wall of the first cylindrical portion 2. At least one support hole 5c having a center on the concentric circle 5b and penetrating in the thickness direction of the guide member 5a is formed. A through hole 5d is formed at the center of the guide member 5a.

  When performing the plasma treatment on the long workpiece W, as shown in FIG. 4, it is supported through the long workpiece W in the support hole 5c and has a high plasma density. The first cylindrical portion 2 is guided to the vicinity of the inner wall.

  By using the plasma processing apparatus 1 according to the first embodiment of the present invention as described above, even when plasma processing is performed using plasma with variations in plasma density, the surface of the long workpiece W is applied to the surface. On the other hand, since plasma processing can be performed by contacting high-density plasma, high-speed plasma processing is possible.

  Further, as shown in FIG. 5, the guide member 5a is provided so that the support holes 5c between the guide members 5a form a predetermined angle with respect to the longitudinal central axis of the first cylindrical portion 2, and each support is provided. When the long workpiece W is supported with respect to the hole 5c, the elongated workpiece W is spirally formed in a region where the plasma density of the first cylindrical portion 2 is high, that is, in the vicinity of the inner wall. Each guide member 5a may be formed in a shape that guides it so as to advance to the right.

  By adopting such a guide member 5a, for example, the second guide member 5a (2) is moved around the longitudinal central axis of the first tubular portion 2 with respect to the first guide member 5a (1). When formed with an inclination of 45 °, the long workpiece W moves from the guide member 5a (1) to the guide member 5a (2), so that high density plasma is generated in the guide member 5a (1). High-density plasma comes into contact with the portion of the outer peripheral surface that is shifted by 45 ° around the central axis from the position of the outer peripheral surface of the long workpiece W that has been in contact. Accordingly, the workpiece W is spirally advanced and passed by the eight guide members 5a disposed in the longitudinal direction of the first tubular portion 2 with an inclination of 45 ° in accordance with (1) to (8). As a result, high-density plasma can be brought into contact with the entire outer peripheral surface of the long workpiece W, so that the surface of the long workpiece can be uniformly and uniformly treated. And

  Furthermore, when the distance between each guide member 5a is the same, it is necessary for the workpiece W to make one round of the inner peripheral surface of the first cylindrical portion 2 by increasing the inclination provided in the guide member 5a. Since the distance to the longitudinal direction of the 1st cylindrical part 2 can be shortened, the plasma processing apparatus 1 can be reduced in size. Specifically, when the inclination is provided at 45 °, eight guide members 5a are required to make one round of the inner peripheral surface of the first tubular portion 2, whereas the inclination is provided at 90 °. The number of guide members 5a may be four to make one round of the inner peripheral surface of the first tubular portion 2, and the length of the first tubular portion 2 in the longitudinal direction can be ½ or less. .

  In the state where the long workpiece W is supported in the support hole 5c of the guide member 5a as shown in FIG. 4, each guide member 5a is rotated by a predetermined angle to obtain a long shape as shown in FIG. The workpiece W may be spirally advanced with respect to the longitudinal direction of the first cylindrical portion 2.

  Moreover, as shown in FIG. 6, it can be set as the 1st cylindrical part 2 by connecting the some unit cylinder 2a. By setting it as the 1st cylindrical part 2 like this, after passing the elongate to-be-processed object W with respect to the support part 5c of the guide member 5a, the unit cylinder 2a is connected, and the 1st cylindrical part 2 is connected. Therefore, even when a material having poor shape stability is processed as the long workpiece W, it can be easily set and the operability of the plasma processing apparatus 1 can be improved. Furthermore, when the guide member 5a is rotated so that the long workpiece W is advanced in a spiral shape, it is easily connected to the unit tube 2a while providing an angle. The object W can be made to advance spirally.

  Further, as shown in FIG. 7, a thin cylindrical insulating tube 6 is formed in a space near the center axis of the first cylindrical portion 2 formed by the through hole 5d of the guide member 5a inside the first cylindrical portion 2. Is inserted and arranged. The plasma generation gas is introduced only into the space formed by the outer peripheral surface of the insulating tube 6 and the inner wall of the first cylindrical portion 2 to generate plasma, thereby reducing the amount of plasma generation gas used. The running cost can be reduced by suppressing the running cost.

  Moreover, since the temperature of the plasma can be prevented by introducing a coolant such as cooling water into the insulating tube 6, the plasma treatment is also performed on the long workpiece W that is weak against heat. Can do.

Next, a second embodiment of the plasma processing apparatus 1 of the present invention will be described.
In the second embodiment of the present invention, as shown in FIG. 8, the ring-shaped electrode 3 is formed so as to extend over the entire length of the outer peripheral surface of the first cylindrical portion 2, and the inside of the insulating tube 6 is made of copper. A conductive material 7 made of a cylindrical rod is inserted in close contact with the inner wall of the insulating tube 6. At this time, a plasma generating gas is introduced into a space formed by the inner wall of the first tubular portion 2 and the outer peripheral surface of the insulating tube 6, and power is supplied to the ring-shaped electrode 3 and the conductive material 7 using the power source P. And generating a dielectric barrier discharge by applying a voltage so as to provide a potential difference in the radial direction of the first cylindrical portion, thereby generating plasma.

  In a space formed by the inner wall of the first tubular portion 2 and the outer peripheral surface of the insulating tube 6, a plurality of guide members 5a are arranged in the longitudinal direction, and the long workpiece W is placed in the space. It is designed to support and guide.

  In the second embodiment, the conductive material 7 has been described as a copper cylindrical rod. However, in order to efficiently generate a discharge, the adhesion between the inner wall of the insulating tube 6 and the outer peripheral surface of the conductive material 7 is improved. The height is important, and it is more preferable to use, for example, an aqueous electrolyte solution such as a sodium chloride aqueous solution or seawater or a conductive liquid such as mercury as the conductive material 7, and the adhesion to the inner wall of the insulating tube 6 is extremely high. Thus, dielectric barrier discharge can be generated efficiently.

  In addition, the conductive liquid is formed to always flow inside the insulating tube 6. For example, a tank for storing a conductive liquid is provided, the conductive liquid is introduced from the tank into the insulating tube 6, and the conductive liquid is led from the inside of the insulating tube 6 to the tank. It is preferable to circulate the conductive liquid inside the insulating tube 6. By always flowing a conductive liquid, it can be cooled while supplying power, and an effect as a refrigerant can also be expected. In addition, the effect as a refrigerant | coolant can further be improved by cooling a conductive liquid in a tank or a flow path.

  By using the plasma processing apparatus 1 of the second embodiment as described above, it is possible to form a region where the plasma is denser, and to uniformly treat the long workpiece W at high speed uniformly. Can be applied.

<Example 1>
Examples using the plasma processing method of the present invention will be described below.
Using the plasma processing apparatus 1 of the present invention, the long workpiece W was subjected to plasma processing, and the processing effect was examined.

  For the long workpiece W, a polyamide monofilament having a diameter of 0.243 mm (an 85/15 copolymer of nylon 6 and Nylon 66), a polyvinylidene fluoride monofilament having a diameter of 0.268 mm, and A 400 denier / 384 filament ultrahigh molecular weight polyethylene fiber made by combining four 100 denier / 96 filament ultrahigh molecular weight polyethylene fibers was used.

<How to create a sample>
The following describes how to create a detailed sample.
The long workpiece W is provided by two yarn feed rolls with a nip roller provided with a predetermined plasma processing apparatus installation range (in this embodiment, an installation range of about 1 m is provided). The unprocessed long workpiece W is set so as to be conveyed from the raw yarn bobbin wound with the winding bobbin.

  In order to clarify the processing effect of the plasma processing apparatus 1 of the present invention, in addition to the plasma processing apparatus 1 of the present invention, a multi-gas plasma jet processing apparatus (multi-gas plasma manufactured by Plasma Concept Tokyo Co., Ltd.) is used for comparison. These were disposed in the plasma processing apparatus installation range, and the plasma treatment was performed on the long workpiece W.

  The aspect of each plasma processing apparatus will be described.

  The plasma processing apparatus 1 of the present invention uses the apparatus of the embodiment shown in FIG. 1, and a plurality of ring-shaped electrodes 3 made of copper are each about 1 cm on a first cylindrical part 2 made of a glass tube having a diameter of 3 mm and a length of 1 m. A plasma irradiation range of about 18 cm arranged at intervals was formed. A plasma generation gas introduction portion 4 for introducing a plasma generation gas is formed on one end side (the right end in FIG. 1) of the first cylindrical portion 2, and on the other end side of the first cylindrical portion 2. In order to suppress discharge of the plasma generating gas, an adhesive film (not shown) is provided so as to narrow the opening. Electric power is applied to each of the plurality of ring electrodes 3 from a power supply device, and a voltage is applied so that a potential difference is provided in the longitudinal direction of the first cylindrical portion 2.

  A comparative multi-gas plasma jet processing apparatus includes a plastic tube having a diameter of 8 mm and a length of 1 m provided with a plasma inlet at a substantially central portion in the longitudinal direction, and the multi-gas plasma jet generator is injected into the plasma inlet. By connecting the ports, the plasma is introduced so that the plasma flows in opposite directions toward both ends of the plastic tube inside the tube.

  The plasma treatment to the workpiece is performed by introducing the long workpiece W drawn from the raw yarn bobbin from one end of the plastic tube and treating the long workpiece to be processed from the other end. The surface of the long workpiece W inside the plastic pipe while being transported from the raw yarn bobbin to the winding bobbin at a predetermined transport speed by deriving the object W and winding it on the winding bobbin. Is performed by bringing a plasma into contact with the substrate.

  A single gas or mixed gas of argon gas, helium gas, oxygen gas and carbon dioxide gas was used as the plasma generating gas.

  A sample for measuring the treatment effect is prepared by winding a long processed object W after treatment on a winding bobbin so that there is no space between the yarns and winding them around a single layer. . In this example, a bobbin having a diameter of 50 mm and a winding width of 65 mm was used as the winding bobbin.

<Measurement method of contact angle>
A method for measuring the contact angle of the sample will be described.
A portable contact angle meter PG-X manufactured by FIBROsystemAB (Sweden) was used as the measurement apparatus. In the measurement, a measuring device was set on the yarn on which the samples were aligned and wound, and pure water was dropped on the yarn to detect the contact angle between the aligned yarn row and pure water. In addition, a contact angle shows that it is a hydrophilic surface, so that a value is small, and it shows that it is a water-repellent surface, so that a value is large.

  First, using a multi-gas plasma jet processing apparatus, the difference in the processing effect depending on the gas type on each object to be processed was examined. Table 1 shows the results of the gas type, gas flow rate, sample transport speed, and contact angle before / after treatment used for plasma treatment of each sample. In the table, F1 represents a polyamide monofilament, F2 represents a polyvinylidene fluoride monofilament, and F3 represents an ultrahigh molecular weight polyethylene fiber.

When the material is polyamide monofilament as F1, No. in Table 1 As shown in FIG. 1, the contact angle before the treatment was 81.7 ° by performing the plasma treatment using the plasma generation gas in which the oxygen gas 1 volume% was added to the argon gas 100 volume%. On the other hand, the contact angle after the treatment was 0.0 °, and a high hydrophilic effect was obtained.
No. 2 and no. As shown in FIG. 3, when the plasma treatment was performed using a plasma generation gas in which 1% by volume of carbon dioxide gas was added to 100% by volume of helium gas, No. 3 with a gas flow rate of 5 L / min. In No. 2, the contact angle before the treatment was 81.7 °, the contact angle after the treatment was 69.3 °, a slight hydrophilizing effect was observed, and the gas flow rate was 10 L / min. In No. 3, the contact angle before the treatment was 81.7 °, and the contact angle after the treatment was 0.0 °, and a high hydrophilic effect was recognized.
No. 4 and no. As shown in FIG. 5, when the plasma treatment was performed using a plasma generating gas in which 1 volume% of oxygen gas was added to 100 volume% of the herim gas, No. 5 having a gas flow rate of 5 L / min. In No. 4, the contact angle before the treatment was 81.7 °, the contact angle after the treatment was 67.7 °, a slight hydrophilizing effect was observed, and a gas flow rate of 10 L / min. In No. 5, the contact angle before the treatment was 81.7 °, and the contact angle after the treatment was 85.7 °.

When the material is polyvinylidene fluoride monofilament as F2, No. As shown in FIG. 6, the contact angle before the treatment was 91.7 ° by performing the plasma treatment using the plasma generation gas in which the oxygen gas 1 volume% was added to the argon gas 100 volume%. On the other hand, the contact angle after treatment was 99.9 °, indicating that the contact angle was large, and a water repellency effect was obtained.
No. As shown in FIG. 7, when plasma treatment is performed using a plasma generation gas in which 1% by volume of carbon dioxide gas is added to 100% by volume of helium gas, the contact angle before treatment is 91.7 °, A slight hydrophilizing effect was observed with a contact angle of 77.2 °.
Conversely, no. As shown in FIG. 8, when plasma processing is performed using a plasma generating gas in which 1% by volume of oxygen gas is added to 100% by volume of helium gas, the contact angle before processing is 91.7 °, When the subsequent contact angle was 96.3 °, the contact angle increased and the water repellency effect was observed.

  Similarly, when the raw material was ultra-high molecular weight polyethylene fiber as F3, it showed hydrophilicity before the treatment, and it penetrated in about 1 second 30 when pure water was dropped. No. 9 and no. As shown in FIG. 10, by performing plasma treatment using a plasma generation gas of carbon dioxide gas 100 volume% and argon gas 100 volume%, the result shows that the dripped pure water is so hydrophilic that it permeates in an instant. became.

  Next, using the plasma processing apparatus of the present invention or the comparative multi-gas plasma jet processing apparatus, the contact angle is measured when the polyamide monofilament (F1) and the polyvinylidene fluoride monofilament (F2) are subjected to plasma processing. The processing effect of the plasma processing apparatus of the present invention was examined. Table 2 shows the results of measurement of the processing apparatus, gas type, gas flow rate, sample transport speed, and contact angle before / after processing used for processing each sample.

  When the material is polyamide monofilament as F1, No. in Table 2 Ny1 and No. As shown by Ny2, in the samples subjected to the plasma treatment using either the plasma treatment device of the present invention or the comparative multi-gas plasma jet treatment device, the contact angle before the treatment is 81.7. The hydrophilization effect was recognized with a contact angle of 0.0 ° after treatment. However, in the sample processed using the comparative multi-gas plasma jet processing apparatus, since the contact angle of the water droplets was uneven, it was considered that the object was not uniformly processed uniformly. It is done. On the other hand, in the sample using the plasma processing apparatus of the present invention, such unevenness in the contact angle of water droplets was not recognized, and the surface of the object to be processed could be uniformly treated.

  Similarly, when the material is a polyvinylidene fluoride monofilament as F2, No. FC1 and No. As shown in FC2, in the sample subjected to the plasma treatment using the plasma treatment apparatus of the present invention, the contact angle before treatment is 91.7 °, the contact angle after treatment is 0.0 °, and high hydrophilization. While the effect was recognized, in the sample using the comparative multi-gas plasma jet processing apparatus, the contact angle before the treatment was 91.7 ° and the contact angle before the treatment was 96.3 °. As a result, the contact angle increased.

  From the above results, it has been clarified that by using the plasma processing apparatus of the present invention, it is possible to uniformly and uniformly perform plasma processing on an object to be processed, and a high surface modification effect can be obtained.

  Further, using polyvinylidene fluoride monofilament as the material F2, pure water for the sample when the plasma treatment is performed by changing the conveyance speed of the object to be treated in order to examine the treatment effect in the plasma treatment apparatus of the present invention. The contact angle results of No. FC1, No. FC3 and No. This will be described using FC4.

  When the transfer speed is 5 m / min or 10 m / min, No. FC1 and No. As shown in FC3, the contact angle before treatment was 91.7 °, whereas the contact angle after treatment was 0.0 °. FC1 and No. In both FC3, high hydrophilization effect was recognized so that pure water could permeate in an instant. Furthermore, when the conveyance speed is increased to a conveyance speed of 20 m / min, no. As shown in FC4, although the contact angle before treatment was 91.7 ° and the contact angle after treatment was 75.1 °, a slight hydrophilic effect was observed, but surface modification until pure water penetrated It did not reach. From this result, it can be seen that the longer the plasma irradiation time to the object to be processed, the higher the surface modification effect.

  Thus, by using the plasma processing apparatus of the present invention, it is possible to obtain a high surface modification effect on the long workpiece W. Furthermore, a uniform and uniform plasma treatment can be performed on the surface of the workpiece.

In addition, a third embodiment of the plasma processing apparatus 1 of the present invention will be described.
In the third embodiment of the present invention, as shown in FIG. 9, for example, plasma is stably generated even when a plasma treatment is performed on a long workpiece W having electrical conductivity such as tungsten or steel. In addition, the embodiment was invented to enable good plasma processing, and at least one second cylindrical portion integrally formed so as to penetrate perpendicularly to the first cylindrical portion 2. 8 is provided. Further, by introducing a plasma generating gas from the plasma generating gas introducing portion 4 into the first cylindrical portion 2 and applying a voltage so as to provide a potential difference in the longitudinal direction with respect to the ring-shaped electrode 3, Plasma generated inside the first cylindrical portion 2 is introduced into the second cylindrical portion 8.

  In addition, by providing a plug that can be freely opened and closed in the second cylindrical portion 8, it is possible to perform plasma processing on the long object to be processed in the first cylindrical portion 2.

  At this time, in the ring-shaped electrode 3, as shown in FIG. 9, the ring-shaped electrode 3 disposed at a position adjacent to the second cylindrical portion 8 is preferably grounded. Even when the elongated workpiece W having electrical conductivity passes through the portion where the first cylindrical portion 2 intersects, abnormal discharge occurs because the adjacent ring-shaped electrode 3 is in the grounded state. In this way, plasma can be stably generated and introduced into the second cylindrical portion 8.

  Further, it is preferable that the plasma generating gas introducing portions 4 are provided at both ends of the first cylindrical portion 2 respectively, and the second cylindrical portion 8 is made to flow by the flow of the plasma generating gas introduced from both sides. Since the plasma generated in this way can be easily introduced and a higher density plasma can be introduced into the second cylindrical portion 8, plasma processing can be performed on the long workpiece W at high speed. Can be applied.

  Further, when a plurality of second cylindrical portions 8 are provided for the first cylindrical portion 2, as shown in FIG. 10, between the second cylindrical portion 8 and the second cylindrical portion 8. Therefore, it is preferable to further provide a plasma generation gas introduction portion 4 for introducing a plasma generation gas at the center so that a pair of ring-shaped electrodes 3 are provided on both sides.

  In the case of adding a gas such as oxygen gas, carbon dioxide gas and hydrogen gas in order to improve the processing effect to the plasma generating gas, or when adding a deposit for the purpose of chemical vapor deposition, the second cylindrical shape is used. It is preferable to perform the plasma treatment so as to be directly introduced into the portion 8.

  Further, when the first cylindrical portion 2 is formed by connecting a plurality of unit cylinders 2a in the longitudinal direction, the first cylindrical portion 2 and the second cylindrical portion 8 intersect as shown in FIG. A cross-shaped connecting member 9 is provided in the portion to be connected, and the unit tube 2a is connected to a pair of openings 9a, 9c facing the connecting member 9 to form the first cylindrical portion 2, and the connecting member 9 is opposed to the unit tube 2a. The other pair of openings 9b, 9d is configured as the second cylindrical portion 8. In this way, by forming the plasma processing apparatus 1 by connecting the unit cylinder 2a and the connecting member 9, after passing the long workpiece W through the unit cylinder 2a and the connecting member 9, the unit cylinder 2a. Since the plasma processing can be performed by connecting the connecting member 9 and the connecting member 9 so that the plasma processing can be performed, the plasma processing apparatus having excellent operability can be obtained.

  By using the plasma processing apparatus 1 of the third embodiment of the present invention as described above, the first cylindrical portion 2 passes through the long cylindrical workpiece W having electrical conductivity through the second cylindrical portion 8. Since the generated plasma and the long workpiece W are brought into contact with each other inside the second cylindrical portion 8 and the long workpiece W is subjected to plasma treatment, the electrical conductivity is increased. It is possible to suppress abnormal discharge between the long object to be processed W and the ring-shaped electrode 3, generate plasma stably, and have a long object to be electrically conductive. Plasma processing to W can be easily performed.

  In addition, a fourth embodiment of the plasma processing apparatus 1 of the present invention will be described. In the fourth embodiment of the present invention, as shown in FIG. 12, flat upper electrode 10a and lower electrode 10b, which are arranged to face each other and to which power is applied from power source P, respectively, and upper electrode 10a and lower electrode are applied. Between the insulating plate 11 and the lower electrode 10b, the insulating plate 11 is arranged on the lower surface of the upper electrode 10a between the side electrode 10b and the insulating plate 11 and the lower electrode 10b. Between the pair of spacers 12 that support the insulating plate 11 on the lower electrode 10b and the gap 12a formed by the insulating plate 11 and the lower electrode 10b in a state where a predetermined gap 12a is formed on the long electrode 10b. And a guide unit 5 that guides the workpiece W so as to travel in a region where the plasma density is high.

  The upper electrode 10a is formed with a plasma generating gas inlet 13 for introducing a plasma generating gas, and the insulating plate 11 is introduced from the plasma generating gas inlet 13 formed in the upper electrode 10a. A plurality of plasma generation gas outlets 14 for injecting the generated plasma generation gas into the gap 12a formed between the insulating plate 11 and the lower electrode 10b are opened on the inner surface side of the gap 12a.

  In the plasma processing apparatus 1 of the fourth embodiment, a dielectric barrier discharge is generated by applying power from the power source P to the upper electrode 10a and the lower electrode 10b with the plasma generation gas introduced. Plasma is generated in a gap 12a formed by the insulating plate 11 and the lower electrode 10b.

  In the plasma processing apparatus 1 of the fourth embodiment as described above, the density in the gap 12a located near the center of the range where the upper electrode 10a and the lower electrode 10b overlap is high, and from the center toward the outer circumferential direction. Plasma is formed such that the density gradually decreases.

  For this reason, as shown to Fig.13 (a) and (b), the guide part 5 has the some annular | circular shaped holding | maintenance part 15a which forms the conveyance path | route of the elongate to-be-processed object W, and each holding | maintenance part 15a. Of the insulating plate 11 and the lower electrode so as to allow the long workpiece W to pass through the region where the plasma density is high. 10b is located at the center in the longitudinal direction (left and right in the paper direction in FIG. 13A) of the overlapping range, and at least near the approximate center of the overlapping range of the upper electrode 10a and the lower electrode 10b.

  The guide member 15 is not limited to this embodiment. For example, the guide member 15 may be a thin plate with a plurality of round through holes, a comb-like thin plate with a half-moon-shaped recess, or a circular tube. Any shape can be used as long as the holding portion 15b can hold a long workpiece W such as a U shape or a Y shape.

  By using the plasma processing apparatus 1 according to the fourth embodiment of the present invention as described above, even when plasma processing is performed using plasma with variations in plasma density, the surface of the long workpiece W is applied to the surface. On the other hand, high-density plasma processing is possible by bringing high-density plasma into contact.

  Furthermore, by using a known rotating device, the long workpiece W is transported while being rotated so as to be twisted around the conveyance direction axis of the long workpiece W, so that the long workpiece W A uniform and uniform surface treatment can be applied to the surface of the workpiece W.

  Moreover, the long object which performed the plasma process using the plasma processing apparatus 1 of this invention is very excellent in affinity with a dyeing agent or a resin coating agent, and the dyeing | staining and resin coating which were given to the surface of the long object It is possible to provide fishing lines and fibers with less peeling.

<Example 2>
The plasma processing apparatus 1 according to the fourth embodiment of the present invention is used to perform plasma processing on the long workpiece W and to apply a surface treatment agent, so that the abrasion resistance effect of the surface treatment agent by the plasma treatment is applied. Was examined.

  As the long workpiece W, a nylon monofilament having a circular cross section with a diameter of 0.33 mm was used. The processing conditions in the plasma processing apparatus 1 are as follows: the gap 12a is 2 mm, the applied voltage is 35 kV, the frequency is 200 Hz, oxygen gas is used as the plasma generation gas, and the long workpiece W is transported at a speed of 10 m / min. Was given. Moreover, the emulsion liquid (Marposal coat EX-5G, Matsumoto Yushi Seiyaku Co., Ltd. product) of amino-modified silicone 10% density | concentration was used as a surface treating agent.

  Sample A with the surface modifier applied after the plasma treatment and Sample B with the surface modifier applied without the plasma treatment were subjected to a casting test with a fishing rod, and were cast 0, 50, 100, and 300 times. Table 3 shows the results of measuring the contact angle of pure water to sample A and sample B later.

  As shown in Table 3, the samples with no casting test showed very excellent water repellency, with a contact angle of 110 ° and a contact angle of 107 °, for both Sample A and Sample B. Thereby, it can be seen that in both sample A and sample B, the surface modifier made of water-repellent resin is uniformly applied to the surface of the elongated workpiece W.

  After the casting test, Sample A, to which the surface modifier was applied after the plasma treatment, was slightly obtained by performing casting at 94 ° after 50 times casting, 90 ° after 100 times casting, and 94 ° after 300 times casting. Although the water repellency dropped, the water repellency was maintained.

  Sample B coated with the surface modifier without plasma treatment was 62 ° after 50 times casting, 62 ° after 100 times casting, and 60 ° after 300 times casting. It can be seen that the water repellency is greatly impaired.

  From this result, it is shown that the surface modifier applied to the surface of the long workpiece W is worn or peeled off due to friction during casting, and surface modification is performed using the plasma processing apparatus 1 of the present invention. It was revealed that the adhesiveness between the long workpiece W and the surface modifier is significantly improved by performing the plasma treatment before applying the agent.

  In addition, in sample A in which the surface modifier is applied after the plasma treatment, even when casting is repeated, the feeling of slipping and water repellency of the yarn is not impaired, and a good feeling of use such as excellent yarn release feeling during casting is also obtained. It turns out that it is obtained.

  The plasma processing apparatus of the present invention is not limited to the first to fourth embodiments, and various modifications can be made without departing from the features of the present invention. For example, the first embodiment In the second embodiment, the guide member 5a is described as a shape in which a plurality of support holes 5c are formed in a disk. However, a ceramic snare type is provided on the circumferential portion of the inner wall of the first cylindrical portion 2. You may form so that the elongate to-be-processed object W may be guided by installing the existing thread path guide of a dock tail type or a loop type.

  Further, for example, in the fourth embodiment, the plasma generation gas inlet 13 may be formed in the lower electrode 10b, and the plasma generation gas may be introduced into the gap 12a from the lower electrode 10b side. 11 and the lower electrode 10b are formed so as to open plasma generating gas inlets 13 for introducing a plasma generating gas into the inner surface of the gap 12a side from both sides of the upper electrode 10a and the lower electrode 10b. A plasma generating gas may be introduced.

DESCRIPTION OF SYMBOLS 1 Plasma processing apparatus 2 1st cylindrical part 2a Unit cylinder 3 Ring-shaped electrode 4 Plasma generation gas introduction part 5 Guide part 5a Guide member 5b Concentric circle 5c Support hole 5d Through-hole 6 Insulating tube 7 Conductive material 8 Second cylindrical part DESCRIPTION OF SYMBOLS 9 Connection member 9a, 9b, 9c, 9d Opening part 10a Upper electrode 10b Lower electrode 11 Insulating plate 12 Spacer 12a Gap 13 Plasma generating gas introduction port 15 Guide member 15a Holding part W Long-form to-be-processed object P Power supply

Claims (1)

A flat plate-like upper electrode that generates plasma having a density distribution that is disposed opposite to each other and has the highest density in the vicinity of the center of the overlapping range in plan view and gradually decreases in the outer circumferential direction; A lower electrode;
On the lower surface of the upper electrode between the upper electrode and the lower electrode, an insulating plate disposed so as to cover at least the entire lower surface of the upper electrode;
A pair of parallel plates disposed in parallel with the conveying direction of the long workpiece, and supporting the insulating plate on the lower electrode in a state where a predetermined gap is formed between the insulating plate and the lower electrode. Spacers,
The plasma has a high plasma density in the gap, and is provided at least in the center in the conveying direction of the long workpiece, and the long workpiece in the gap advances through the high plasma density region. And a guide portion for guiding
At a position where the upper electrode and the lower electrode face each other, at least one of the insulating plate and the inner surface on the gap side of the lower electrode, a plasma generating gas for introducing a plasma generating gas into the gap The inlet is open,
The guide portion may have a single or plurality of holders forming the conveying path of the elongated object to be processed,
A plasma processing apparatus, comprising: a rotating device that rotates the long workpiece to be twisted about a conveyance direction axis with respect to the long workpiece to be conveyed.

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